Synthesis and application of novel P-chiral monophosphorus ligands

Xie, Xiaoyi; Li, Sanliang; Chen, Qiaoyu; Guo, Hao; Yang, Junfeng; Zhang, Junliang

doi:10.1039/d1qo01819a

Cited by 21 publications

(5 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The addition of the secondary phosphine oxide to terminal and internal alkynes produced alkenylphosphine oxides 29 in good to excellent chemo-, regio-, and enantioselectivities and recovered secondary phosphine oxides. The practicability of this method was extended to the subsequent base-mediated cyclization of P-chiral o -methylphenyl alkenylphosphine oxides 31 to build a class of novel P-chiral monophosphine compounds based on the dihydrobenzophosphole backbone (called Xie-Phos) . Then, we found that palladium/Xiao-Phos ( X1 or X2 ) efficiently catalyzed the kinetic resolution reaction of racemic secondary phosphine oxides via P-benzylation, simultaneously affording P-chiral tert - and sec -phosphine oxides 30 in good yields with high enantioselectivities (a selectivity factor of up to 226.1) …”

Section: Coupling Reactionsmentioning

confidence: 99%

Sadphos as Adaptive Ligands in Asymmetric Palladium Catalysis

Li,

Zhang

2024

Acc. Chem. Res.

Self Cite

View full text Add to dashboard Cite

Section: Coupling Reactionsmentioning

confidence: 99%

Sadphos as Adaptive Ligands in Asymmetric Palladium Catalysis

Li,

Zhang

2024

Acc. Chem. Res.

Self Cite

View full text Add to dashboard Cite

“…Figure presents all the P-stereogenic monophosphorus ligands reported from 2001 to 2023. ,,,,,,,,,,− …”

Section: A Historical Overview Of P-stereogenic Phosphorus Ligandsmentioning

confidence: 99%

P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Imamoto

2024

Chem. Rev.

View full text Add to dashboard Cite

Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality ligands and P-stereogenic phosphorus ligands. Most of the reported ligands belong to the former class. Privileged ones such as BINAP and DuPhos are frequently employed in a wide range of catalytic asymmetric transformations. In contrast, the latter class of P-stereogenic phosphorus ligands has remained a small family for many years mainly because of their synthetic difficulty. The late 1990s saw the emergence of novel P-stereogenic phosphorus ligands with their superior enantioinduction ability in Rh-catalyzed asymmetric hydrogenation reactions. Since then, numerous P-stereogenic phosphorus ligands have been synthesized and used in catalytic asymmetric reactions. This Review summarizes P-stereogenic phosphorus ligands reported thus far, including their stereochemical and electronic properties that afford high to excellent enantioselectivities. Examples of reactions that use this class of ligands are described together with their applications in the construction of key intermediates for the synthesis of optically active natural products and therapeutic agents. The literature covered dates back to 1968 up until December 2023, centering on studies published in the late 1990s and later years.

show abstract

“…In 2022, this protocol was employed by the same group to assemble a set of novel P-chiral monophosphorus ligands (Xie-phos) 14. [10] The benzophospholane framework was rapidly synthesized via a simple base-mediated intramolecular cyclization from P-stereogenic adducts 12. The obtained products 14 served as efficient ligands in many catalytic asymmetric reactions (such as α-arylation of amides and the domino Heck/Suzuki reaction).…”

Section: Asymmetric Addition To Activated Alkenes or Alkynesmentioning

confidence: 99%

Research Progress on Catalytic Asymmetric Synthesis of P-Chiral Compounds

Li¹,

Yin²

2022

Chinese Journal of Organic Chemistry

View full text Add to dashboard Cite

P-Chiral compounds are a valuable class of privileged structures in pharmaceutically and biologically active compounds and also serve as powerful and versatile ligands or organocatalysts in asymmetric synthesis. Therefore, their asymmetric synthese has gained increasing attention in the past two decades. By means of kinetic resolution (KR) or dynamic kinetic resolution (DKR) strategy, racemic secondary phosphines, their borane-adducts or their oxides can be transformed to the associated compounds with P-chirality, which serves as a straightforward and efficient protocol to construct a P-chiral center. The recent achievements of the transition-metal-catalyzed asymmetric syntheses of P-chiral compounds based on KR and DKR of racemic secondary phosphines, their borane-adducts and their oxides in the past two decades are summarized. Meanwhile, arylation, addition to activated alkenes or alkynes, alkylation and other reactions are covered respectively based on the varied reaction partners. These reaction entails the formation of new P-C, P-O and P-N bonds in an asymmetric manner. What's more, the transformation of prochiral primary phosphines to P-chiral secondary phosphines is mentioned in the miscellaneous reaction section.

show abstract

Synthesis and application of novel P-chiral monophosphorus ligands

Abstract: A series of novel P-stereogenic monophosphorus ligands (Xie-phos) were synthesized via the hydrophosphinylation of alkynes with secondary phosphine oxides by palladium catalysis and the following base mediated cyclization.

Cited by 21 publications

References 34 publications

Sadphos as Adaptive Ligands in Asymmetric Palladium Catalysis

Sadphos as Adaptive Ligands in Asymmetric Palladium Catalysis

P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Research Progress on Catalytic Asymmetric Synthesis of P-Chiral Compounds

Contact Info

Product

Resources

About